CN112237850B - Membrane and preparation method and application thereof - Google Patents
Membrane and preparation method and application thereof Download PDFInfo
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- CN112237850B CN112237850B CN201910656442.4A CN201910656442A CN112237850B CN 112237850 B CN112237850 B CN 112237850B CN 201910656442 A CN201910656442 A CN 201910656442A CN 112237850 B CN112237850 B CN 112237850B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention provides a method for preparing a membrane, which comprises the steps of mixing a metal organic framework material with a polymer and a pore canal protective agent, and carrying out melt stirring at a first temperature until the mixture is uniform to obtain a melt mixture; carrying out hot-pressing treatment on the uniformly mixed molten mixture at a second temperature and a first pressure to obtain a formed initial metal organic framework film; and cooling the initial metal organic framework membrane to room temperature, soaking and washing the initial metal organic framework membrane by using a pore canal protective agent remover, and drying to obtain the metal organic framework membrane. The method can be used for preparing the metal organic framework film with large load capacity, and the prepared metal organic framework film has high pore channel retention rate and excellent selectivity and separation performance. In addition, the preparation method disclosed by the invention is simple to operate, does not use a substrate or a solvent, saves cost and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a preparation method of a metal organic framework membrane, the metal organic framework membrane prepared by the method and application thereof.
Background
The metal organic framework material is a novel nano-pore crystalline material, and the structure of the metal organic framework material is formed by connecting various organic ligands by metal ions or clusters in a strong coordination bond mode. Varying thousands of organic ligands and inorganic components enable the metal-organic framework to form a wide variety of topologies and satisfactory structures. Since the metal-organic frameworks themselves have many advantages: the size of the aperture is adjustable, the specific surface area is very high, the functionality is strong, the size is adjustable, and the like, and all the advantages enable the metal organic framework membrane containing the metal organic framework material to be an ideal material in membrane separation engineering. The metal-organic framework film can be classified into a metal-organic framework crystal film and a metal-organic framework mixed matrix film.
The metal organic framework crystal film is a metal organic framework porous film continuously grown on a carrier and can be prepared by methods such as an in-situ growth method, an LBL deposition method, a seed crystal method, an ultrasonic chemical method and the like. The in-situ growth method is to directly put a substrate for film formation into a reaction solution to grow metal-organic framework crystals on the surface of the substrate, and has the advantages of simple operation, long reaction time, easy occurrence of film defects, excessive impurities and difficult mass production expansion; the LBL deposition method is that organic groups are pre-modified on the surface of a substrate, then the substrate is placed in a metal solution and an organic ligand solution in turn, and the metal organic skeleton film is obtained by layer growth; the seed crystal method is to pre-coat seed crystal on the surface of the substrate, and then to put the substrate in-situ growth in the reaction solution to form a film, the method makes up the defects of easy occurrence of film defects and excessive impurities in the in-situ growth method to a certain extent, but still has the problems of longer reaction time and difficult realization of mass production compared with the method of the invention; the ultrasonic chemistry method is a new method developed in recent years, and is to carry out ultrasonic treatment on a reaction solution with a substrate to produce a metal organic framework film, and the method has the advantages of mild reaction conditions (the reaction can be carried out at normal temperature) and quicker reaction compared with other methods, but the product of the method often has a large number of defects, insufficient purity and large mass production difficulty. In general, the current preparation methods have long production cycle, insufficient mass production capacity, low yield, high relative production cost, and require the presence of a substrate in the preparation of the metal-organic framework film.
In addition, the mixed matrix membrane is formed by the polymer and the inorganic filler dispersed in the polymer, combines the advantages of easy processing of the polymer membrane and high separation performance of the inorganic membrane, and is an important development direction of the high-performance separation membrane. The metal-organic framework mixed matrix film reported at present is mostly obtained by casting, and is usually prepared by directly mixing metal-organic framework crystals with a polymer solution. The organic solvent is needed in the preparation process, which is high in cost and is not beneficial to the environment. The metal organic framework membrane prepared by the method has lower metal organic framework loading capacity, and in the production process, the pore canal of the metal organic framework material is easily filled with polymer, so that the specific surface area is reduced, the separation effect is poor and the membrane flux is small in the separation process.
Disclosure of Invention
The present invention addresses the above problems by providing a novel method for producing a film, comprising:
(1) Mixing a metal organic framework material with a polymer and a pore canal protective agent, and melting and stirring at a first temperature until the mixture is uniform to obtain a molten mixture;
(2) Carrying out hot-pressing treatment on the uniformly mixed molten mixture at a second temperature and a first pressure to obtain a formed initial metal organic framework film;
(3) Cooling the initial metal organic framework membrane to room temperature, soaking and washing the initial metal organic framework membrane by using a pore canal protective agent remover, and drying to obtain the metal organic framework membrane;
the addition amount of the pore canal protective agent is 2-5 times of the mass of the metal organic framework material, the first temperature is above the melting temperature of the polymer, the second temperature is 80-130 ℃, the first pressure is 0.2-1MPa, and the pore canal protective agent remover is used for removing the pore canal protective agent in the initial metal organic framework film so as to release pore canal in the film.
Preferably, the pore canal protective agent comprises at least one of paraffin oil, soybean oil, polyethylene glycol, glyceryl triacetate and methyl phthalate.
Preferably, the pore canal protective agent remover comprises at least one of ethanol and methylene dichloride.
Preferably, the hot press treatment in the step (3) includes twin-roll hot press, plate hot press, and electric iron.
Preferably, the metal element in the metal-organic framework material comprises at least one of Mg, ca, ce, nd, sm, gd, ti, zr, V, cr, mo, mn, fe, co, ni, cu, ag, zn, cd, al, in.
Preferably, the organic ligands in the metal organic framework material comprise nitrogen coordinated and oxygen coordinated ligands.
More preferably, the organic ligand comprises at least one of trimesic acid, 2, 5-dihydroxyterephthalic acid, 1,3, 5-tris (4-carboxyphenyl) benzene, 2-amino-terephthalic acid, 2-methylimidazole.
Preferably, the polymer comprises at least one of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polysulfone, polyamide resin, polycarbonate, polylactic acid, polyethylene terephthalate, polyvinylidene fluoride.
More preferably, the polymer comprises polyethylene, polyvinylidene fluoride, polylactic acid.
More preferably, the polyethylene is a high density polyethylene.
More preferably, the polyethylene is ultra high molecular weight polyethylene.
Preferably, the first temperature does not exceed 300 ℃.
Preferably, the mass content of the metal organic framework material in the metal organic framework film is 50-90%.
More preferably, the mass content of the metal organic framework material in the metal organic framework film is 70-90%.
Preferably, the method further comprises the following steps before step (1): and (3) performing activation treatment on the metal organic framework material to remove unreacted raw materials and solvents remained in the pore canals of the metal organic framework material.
The invention also provides a film prepared by the above method.
The invention also provides the use of the film prepared by the above method for removing dye.
The preparation method of the invention has simple operation, is easy to realize industrial production, and does not need a substrate and a solvent for dissolving the polymer in the preparation process, thereby saving the cost and being beneficial to environmental protection. The content of the metal organic framework material in the prepared membrane can be adjusted according to practical application, the membrane with higher load content can be obtained by using the method provided by the invention, and the pore canal of the metal organic framework material in the membrane is kept good. When the loading of the membrane is 90%, compared with the raw material metal organic framework material, the pore canal retention rate can reach more than 80%. The prepared membrane has high membrane flux and high selectivity, and has excellent separation effect in removing impurities such as dye in water.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention.
FIG. 1 is a schematic diagram of a filtration system in a dye removal test.
FIG. 2 is a scanning electron micrograph and an X-ray powder diffraction pattern of the film of example 1.
FIG. 3 is a scanning electron micrograph and an X-ray powder diffraction pattern of the film of example 2.
FIG. 4 is a scanning electron micrograph and an X-ray powder diffraction pattern of the film of example 3.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The terms and the like used in the present invention have meanings commonly understood in the art, and some technical terms and terms used in the present invention are explained and defined below.
The Metal-organic framework (Metal-organic framework) is a functional porous material, is formed by coordination of a Metal source (such as a Metal cluster, a Metal oxide or a Metal salt and the like) and an organic ligand, has the advantages of inorganic and organic porous materials, and has the characteristics of high specific surface area, ordered and repeatable pore channels, rich functional groups, good stability, multiple structures and the like. The metal-organic framework material used in the present invention may be synthesized using a method known in the art, such as a hydrothermal method, a stirring and standing method, an electrolytic method, a spinning method, a microwave method, a hot pressing method, etc. The above-mentioned synthetic methods are described in, for example, katz, M.J. et al A facile synthesis of UiO-66, uiO-67 and their derivatives, chem. Commun. 49, 9449-9451, (2013), park, K.S. et al Exceptional chemical and thermal stability of zeolitic imidazolate, frames. P. Natl. Acad. Sci. U S A, 103, 10186-10191, (2006), li S. et al, creating Lithonium-Ion Electrolytes with Biominmetic Ionic Channels in Metal-Organic frames. DOI: 10.1002/adma. 201707476. The metal-organic framework materials prepared by different synthetic methods can be used in the synthetic methods of the membranes of the present invention, either as described above or in the literature. In addition, the metal organic framework material used in the process of the present invention may also be a commercially available finished product.
The 'pore canal protective agent' of the invention refers to a substance which is filled in the pore canal of the metal organic framework material in the preparation process of the membrane to prevent the polymer from blocking the pore canal. The pore protecting agent may be removed by a "pore protecting agent remover" described below, thereby exposing pores of the metal-organic framework material in the finally prepared film.
The term "pore canal protecting agent remover" in the present invention refers to a substance capable of removing pore canal protecting agent filled in pores of a metal-organic framework material, thereby exposing the pores.
The "load" of the present invention refers to the mass ratio of the metal organic framework material to the whole membrane.
The high-density polyethylene, also called low-pressure polyethylene, is usually manufactured by using a Ziegler-Natta polymerization method, and is characterized in that the molecular chains have no branched chains, so that the molecular chain is regular in arrangement and has higher density. The process uses ethylene as raw material and oxygen or organic peroxide as initiator to initiate polymerization reaction in a tubular or kettle type low-pressure reactor. It generally has a molecular weight in the range 40000-300000 and a melting point of typically 142 ℃.
The ultra-high molecular weight polyethylene of the present invention is unbranched linear polyethylene with a molecular weight of 150 ten thousand or more. The molecular formula: - (-CH) 2 -CH 2 (-) n-, density: 0.920-0.964g/cm 3 . The heat distortion temperature (0.46 MPa) is 85 ℃,the melting point is 130-136 ℃.
The method for producing the film of the present invention is described in detail below. The proportion or percentage (%) referred to in the present invention refers to the mass proportion or percentage unless otherwise indicated.
The invention discloses a preparation method of a novel film, which comprises the following steps:
(1) Mixing a metal organic framework material with a polymer and a pore canal protective agent, and melting and stirring at a first temperature until the mixture is uniform to obtain a molten mixture;
(2) Carrying out hot-pressing treatment on the uniformly mixed molten mixture at a second temperature and a first pressure to obtain a formed initial metal organic framework film;
(3) And cooling the initial metal organic framework membrane to room temperature, soaking and washing the initial metal organic framework membrane by using a pore canal protective agent remover, and drying to obtain the metal organic framework membrane.
The metal organic framework material is formed by the action of a metal source and an organic ligand. The skilled person can synthesize the metal-organic framework material using known methods as described above in the present invention, the method of preparing the metal-organic framework material not affecting the membranes of the present invention. Commercially available metal organic framework material finished products may also be used. The metal source in the metal organic framework material can be metal clusters, metal oxides, metal ions and the like, and the metal element contained in the metal source is at least one of Mg, ca, ce, nd, sm, gd, ti, zr, V, cr, mo, mn, fe, co, ni, cu, ag, zn, cd, al, in. The person skilled in the art is able to freely select the metal elements contained in the metal source, including but not limited to the elements exemplified above, depending on the use of the film to be produced. When the metal element contained in the metal source is at least one of the above-listed elements, a film is more easily obtained and the morphology is better. The organic ligand may use any ligand known in the art that reacts with a metal source to form a metal organic framework material, which may be a multidentate organic ligand containing oxygen, nitrogen, etc., such as at least one of trimesic acid, 2, 5-dihydroxyterephthalic acid, 1,3, 5-tris (4-carboxyphenyl) benzene, 2-amino-terephthalic acid, 2-methylimidazole.
And mixing the metal organic framework material, the polymer and the pore canal protective agent, and carrying out melt stirring until the metal organic framework material, the polymer and the pore canal protective agent are fully and uniformly mixed to obtain a melt mixture. The polymer may be any polymer that can be formed into a film, preferably a polymer having a melting temperature in the range of 92℃to 255 ℃. When the melting temperature is within the above temperature range, the temperature required for melting the polymer is low, so that on the one hand, the film material is easier to form, and on the other hand, when the volatile pore protecting agent is used, the volatilization of the pore protecting agent can be reduced. The prepared membrane pore canal is kept intact and has excellent separation effect. The polymer may be, for example, any one of polyethylene, polypropylene, high-density polyethylene, ultra-high molecular weight polyethylene, polyvinyl chloride, polystyrene, polysulfone, polyamide resin, polycarbonate, polylactic acid, polyethylene terephthalate, and polyvinylidene fluoride. Preferably polyethylene, polyvinylidene fluoride, polylactic acid, more preferably polyethylene, more preferably high density polyethylene or ultra high molecular weight polyethylene. The prepared film has excellent performance, high mechanical strength and can maintain the characteristics of the metal organic framework material. The temperature of the melt stirring is not more than the melting temperature range of the polymer but not more than the decomposition temperature of the polymer, and preferably the temperature of the melt stirring is not more than the melting temperature of the polymer, and more preferably the temperature of the melt stirring is not more than 300 ℃. The pore passage protecting agent may be filled into the pores of the metal-organic framework material to prevent the polymer from blocking the pores of the metal-organic framework material, and may be removed by the pore passage protecting agent remover to expose the pores. The pore canal protecting agent can be at least one of paraffin oil, soybean oil, polyethylene glycol, glyceryl triacetate and methyl phthalate. The addition amount of the pore canal protective agent is 2-5 times of the mass of the metal organic framework material. The pore canal protective agent in the range can fully protect the pore canal of the metal-organic framework material.
And then carrying out hot pressing treatment on the molten mixture to obtain the formed initial metal organic framework film. The hot press treatment is not particularly limited as long as the molten mixture can be press-molded, and may be, for example, twin-roll hot press, plate hot press, electric iron, or the like. Other suitable autoclave processes may be used in the process of the present invention. When the film to be produced is required to be shaped, a corresponding mold may be used. The temperature of the autoclave is preferably 80-130 ℃. In this temperature range, press molding can be easily performed without causing decomposition of the polymer. The pressure of the autoclave may be appropriately adjusted depending on the apparatus used and the thickness of the film finally produced, and preferably the pressure of the autoclave is 0.2 to 1 MPa.
And then cooling the initial metal organic framework membrane to room temperature, soaking and washing with a pore canal protective agent remover, and drying to obtain the metal organic framework membrane. Wherein the pore canal protecting agent remover is used for removing the pore canal protecting agent in the initial metal organic framework membrane to release the pore canal in the membrane. It may be any substance capable of dissolving the pore protecting agent and is selected correspondingly according to the kind of the pore protecting agent, and may be, for example, ethanol, methylene chloride, or the like.
In addition, before the metal organic framework material, the polymer and the pore canal protective agent are mixed, the metal organic framework material can be subjected to activation treatment to remove unreacted raw materials and solvents remained in the pore canal of the metal organic framework material. The above-mentioned activation method may use any method known to those skilled in the art, for example, impregnating the synthesized metal-organic framework material with methanol, ethanol, methylene chloride, etc., to exchange solvent molecules in the framework channels and unreacted raw materials; heating, vacuumizing, activating and the like. When the activation is performed by the impregnation method, the impregnation time is generally varied from several hours to tens of hours, and the number of impregnation times is 2 or more. And (5) carrying out vacuum drying after impregnation to obtain the activated metal organic framework material. The specific surface area of the material can be tested using a Quantachrome/Anton-Paar fully automated surface and pore size analyzer (model: autosorb-iQ) to verify the activation effect. The metal organic framework material after the activation treatment has high specific surface area and high porosity, and in this case, the surface functional groups, the porosity and the like of the membrane prepared by the method can also be kept at high level.
The method of the invention can prepare the membrane containing any mass content of the metal organic framework material by mixing the metal organic framework material with polymers in different mass proportions. Preferably, the metal-organic framework material is contained in the film of the present invention in a mass content of 50 to 90%, more preferably, the metal-organic framework material is contained in the film in a mass content of 70 to 90%. When the content of the metal-organic framework material is within the above range, the film is excellent in performance.
The membranes prepared according to the present invention may be used as water permeable membranes, for example for removing dyes from solutions and the like. The present application exemplifies the above-mentioned uses of the film of the present invention by the following method. Those skilled in the art will appreciate that the following methods are merely illustrative of the use of the membranes of the present invention and are not intended to limit the membranes of the present invention to the particular uses described in the following methods.
Dye removal
The specific operation flow is as follows:
the experiment may be performed in a filtration system as shown in fig. 1. The effective membrane area in the system is 9cm 2 The cross flow speed is 250L/h. The solution in the pre-filtration vessel 1 is flowed through the osmotic membrane 4 by the pump 2 into the post-filtration vessel 5, and the pressure gauge 3 is used to measure the pressure of the solution. Different dyes were dissolved in ultrapure water to form a stock solution having a concentration of 100 mg/L. Ultrapure water was passed through the permeable membrane 4 by a pump at a pressure of 0.3 MPa for 45 minutes at room temperature, keeping the flux stable. Then, the stock solutions of different dyes are passed through the membrane under the same conditions, and the filtering effect of the membrane material on the different dyes is tested. And comparing the different concentrations of the dye in the stock solution and the solution after permeation, and calculating to obtain the removal rate. Dye concentration was measured by an ultraviolet-visible spectrophotometer (Analytik Jena AG SPECORD PLUS).
Calculation of membrane flux:
LMH=V/StP
wherein LMH represents membrane flux (L/m 2 V, S, t and P represent the cumulative permeation volume (L), the effective area (m) of the membrane, respectively 2 ) Filtration time (h) and pressure (MPa).
Calculation of removal rate:
E%=（C i -C e ）/C i ×100%
wherein E% represents the removal rate, C i And C e Representing the concentration (mg/L) of dye in the stock solution and the post-permeation solution, respectively.
The method for synthesizing the film is specifically described below with examples.
Example 1
With ZrCl 4 Is a metal source, 2-amino terephthalic acid (NH) 2 BDC) is used for preparing a metal-organic framework material for an organic ligand, and methylene dichloride is used for activating the newly prepared metal-organic framework material. 50 parts by mass of the activated metal-organic framework material were mixed with 37.5 parts by mass of high-density polyethylene (Alfa aser Co., ltd.; no. 041731) and 12.5 parts by mass of ultra-high molecular weight polyethylene (Alfa aser Co., ltd.; no. 043951), followed by addition of 100 parts by mass of paraffin oil (sigma Aldrich Co., ltd.; no. M8691). The mixture was stirred for 10 minutes at 160 ℃. Then, the initial film was obtained by performing a plate-type heat and pressure treatment at 80℃and a pressure of 0.5 MPa. After cooling to room temperature, the initial membrane was washed repeatedly with dichloromethane and then dried to give the membrane of example 1, wherein the metal organic framework loading was 50%. Characterization was performed using scanning electron microscopy and X-ray powder diffraction. X-ray powder diffraction, model: bruker D8 advanced, test interval 3-50 degrees, scanning speed 2 degrees per minute; scanning electron microscope model Hitachi S4800, scanning parameters: the accelerating voltage is 5 kilovolts, the working distance is 9.3 millimeters, the magnification is 45 ten thousand times, and the length scale is 1 micrometer. The results are shown in FIG. 2. The percentage of specific surface area of the metal organic framework material and the membrane were tested using a Quantachrome/Anton-Paar fully automated surface and pore size Analyzer (model: autosorb-iQ) and the results are reported in Table 1. Wherein the specific surface area percentage of the film is expressed as a percentage of the specific surface area of the film divided by the specific surface area of the metal organic framework material.
Fig. 2A is a scanning electron microscope image of a film, and it can be seen from the image that the surface of the formed film has a porous structure and a large specific surface area. Fig. 2B is an X-ray powder diffraction diagram, showing that the curve 6 of the prepared film completely coincides with the single crystal simulated curve 7 of the metal organic framework material, indicating that the successful synthesis results in the corresponding metal organic framework structure, and that the metal organic framework material on the film remains in its original structure and is not destroyed.
Example 2
With Cu (NO) 3 ) 2 As a metal source, trimesic acid is used as an organic ligand to prepare a metal organic framework material. The newly prepared metal organic framework material is activated by methylene dichloride. 70 parts by mass of the activated metal organic framework material were mixed with a total of 30 parts by mass of ultra high molecular weight polyethylene (Alfa aser Co., ltd.; no. 043951) and polyvinylidene fluoride (Alfa aser Co., ltd.; no. 044080) (the mass ratio of ultra high molecular weight polyethylene to polyvinylidene fluoride was 2:1), followed by addition of 170 parts by mass of paraffin oil. The mixture was stirred for 10 minutes at 200 ℃. Then, a twin-roll hot press treatment was performed at 120℃and 0.8MPa to obtain an initial film. After cooling to room temperature, the initial film was washed by repeated impregnation with methylene chloride, and then dried to obtain a film of example 2. The metal organic framework loading in the resulting membrane was 70%. Characterization was performed using scanning electron microscopy and X-ray powder diffraction, the model and parameters of the instrument were the same as in example 1, and the results are shown in fig. 3. The percentage of specific surface area of the metal organic framework material and the membrane were tested using a Quantachrome/Anton-Paar fully automated surface and pore size Analyzer (model: autosorb-iQ) and the results are reported in Table 1.
Fig. 3A is a scanning electron microscope image of a film, and it can be seen from the image that the surface of the formed film has a porous structure and a large specific surface area. Fig. 3B is an X-ray powder diffraction diagram, showing that the curve 8 of the prepared film is completely matched with the monocrystal simulation curve 9 of the metal-organic framework material, which shows that the corresponding metal-organic framework structure is obtained by successful synthesis, and the metal-organic framework material on the film keeps the original structure and is not destroyed.
Example 3
By CrO 3 As a metal source, trimesic acid (BTC) is used as an organic ligand to prepare a metal-organic framework material, and methylene dichloride is used to activate the newly prepared metal-organic framework material. 90 parts by mass of activated metal organic framework material and 10 parts by mass of ultra-high molecular weightPolyethylene (Alfa aser company; number: 043951) was mixed, and then 400 parts by mass of soybean oil (Goldfish) and paraffin oil (mass ratio 1:3) were added. The mixture was stirred for 10 minutes at 130 ℃. Then, a twin-roll hot press treatment was performed at 100℃and 0.2MPa to obtain an initial film. After cooling to room temperature, the initial film was washed by repeated impregnation with methylene chloride, and then dried to obtain a film of example 3. The metal organic framework loading in the resulting membrane was 90%. Characterization was performed using scanning electron microscopy and X-ray powder diffraction, the model and parameters of the instrument were the same as in example 1, and the results are shown in fig. 4. The percentage of specific surface area of the metal organic framework material and the membrane were tested using a Quantachrome/Anton-Paar fully automated surface and pore size Analyzer (model: autosorb-iQ) and the results are reported in Table 1.
Fig. 4A is a scanning electron microscope image of a film, and it can be seen from the image that the surface of the formed film has a porous structure and a large specific surface area. Fig. 4B is an X-ray powder diffraction diagram, showing that the curve 10 of the prepared film is completely coincident with the single crystal simulated curve 11 of the metal organic framework material, indicating that the successful synthesis yields the corresponding metal organic framework structure, and that the metal organic framework material on the MOF film remains in its original structure and is not destroyed.
Examples 4 to 9
Examples 4-9 were prepared according to the methods of examples 1-3, and the raw materials and parameters used in each example are set forth in Table 1. Example 9 was the same as example 1 except that the metal-organic framework material was directly mixed with the polymer without the activation treatment.
Comparative example 1
The procedure of example 5 was followed except that no paraffin oil was used.
Comparative example 2
The procedure of example 5 was repeated except that methylene chloride was not used.
TABLE 1
High density polyethylene-Alfa aser company, no.: 041731;
ultra high molecular weight polyethylene Alfa aser company, no.: 043951;
polyvinylidene fluoride-Alfa aser company, no.: 044080;
polylactic acid-Sigma Aldrich, no: 38534;
polyethylene glycol-sigma Aldrich, no: 202398.
as is clear from the examples and comparative examples, the membrane prepared by the method of the invention has excellent membrane forming performance, and the content of the metal organic framework material in the membrane has a large numerical range and can keep good pore channels.
Experimental example 1
The separation removal effect was examined by the dye removal test described above using the film prepared in example 3, and the results are shown in table 2.
TABLE 2
The separation experiment proves that the membrane has excellent separation selectivity.
Claims (16)
1. A method of making a film comprising:
(1) Mixing a metal organic framework material with a polymer and a pore canal protective agent, and melting and stirring at a first temperature until the mixture is uniform to obtain a molten mixture;
(2) Carrying out hot-pressing treatment on the uniformly mixed molten mixture at a second temperature and a first pressure to obtain a formed initial metal organic framework film;
(3) Cooling the initial metal organic framework membrane to room temperature, soaking and washing the initial metal organic framework membrane by using a pore canal protective agent remover, and drying to obtain the metal organic framework membrane;
the method further comprises the following steps before the step (1): activating the metal organic framework material to remove unreacted raw materials and solvents remained in the pore canals of the metal organic framework material;
the addition amount of the pore canal protective agent is 2-5 times of the mass of the metal organic framework material, the first temperature is above the melting temperature of the polymer, the second temperature is 80-130 ℃, the first pressure is 0.2-1MPa, and the pore canal protective agent remover is used for removing the pore canal protective agent in the initial metal organic framework film so as to release pore canal in the film.
2. The method of claim 1, wherein the pore protectant comprises at least one of paraffin oil, soybean oil, polyethylene glycol, glyceryl triacetate, methyl phthalate.
3. The method of claim 1, wherein the pore protectant remover comprises at least one of ethanol and methylene chloride.
4. The method according to claim 1, wherein the hot press treatment in the step (3) comprises twin-roll hot press, plate hot press, electric iron.
5. The method of claim 1, wherein the metallic element in the metal-organic framework material comprises at least one of Mg, ca, ce, nd, sm, gd, ti, zr, V, cr, mo, mn, fe, co, ni, cu, ag, zn, cd, al, in.
6. The method of claim 1, wherein the organic ligands in the metal-organic framework material comprise nitrogen-coordinated and oxygen-coordinated ligands.
7. The method of claim 6, wherein the organic ligand comprises at least one of trimesic acid, 2, 5-dihydroxyterephthalic acid, 1,3, 5-tris (4-carboxyphenyl) benzene, 2-amino terephthalic acid, 2-methylimidazole.
8. The method of claim 1, wherein the polymer comprises at least one of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polysulfone, polyamide resin, polycarbonate, polylactic acid, polyethylene terephthalate, polyvinylidene fluoride.
9. The method of claim 8, wherein the polymer comprises polyethylene, polyvinylidene fluoride, polylactic acid.
10. The method of claim 9, wherein the polyethylene is a high density polyethylene.
11. The method of claim 9, wherein the polyethylene is ultra high molecular weight polyethylene.
12. The method of claim 1, wherein the first temperature is no greater than 300 ℃.
13. The method according to any one of claims 1 to 12, wherein the mass content of the metal-organic framework material in the metal-organic framework film is 50 to 90%.
14. The method according to claim 13, wherein the metal-organic framework material is present in the metal-organic framework film in an amount of 70-90% by mass.
15. A film prepared by the method of any one of claims 1-14.
16. Use of the film of claim 15 for dye removal.
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